JP2011021057A - Heat-resistant resin molded article - Google Patents
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- JP2011021057A JP2011021057A JP2009164773A JP2009164773A JP2011021057A JP 2011021057 A JP2011021057 A JP 2011021057A JP 2009164773 A JP2009164773 A JP 2009164773A JP 2009164773 A JP2009164773 A JP 2009164773A JP 2011021057 A JP2011021057 A JP 2011021057A
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- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000010954 inorganic particle Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims description 14
- -1 polyparaphenylene terephthalamide Polymers 0.000 claims description 8
- 239000004760 aramid Substances 0.000 claims description 7
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 239000010409 thin film Substances 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- LVGKZTVMAHRVFR-UHFFFAOYSA-N 4-(phenoxazine-10-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C2OC2=CC=CC=C21 LVGKZTVMAHRVFR-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、耐熱性樹脂成型体に関し、さらに詳しくは、難燃性、高温下における寸法安定性に優れ、薄い、フィルム、シート、または、平板等の形状としても高い機械的強度を有する耐熱性樹脂成型体に関するものである。 The present invention relates to a heat-resistant resin molded body, and more particularly, heat resistance having excellent mechanical properties even in the form of a thin film, sheet, or flat plate, which is excellent in flame retardancy and dimensional stability at high temperatures. The present invention relates to a resin molded body.
近年、電子機器の高性能化、高機能化、小型化が急速に進んでおり、電子機器に用いられる電子部品の高密度化、小型化、薄型化の要請が高まっている。これに伴い、電子部品の素材についても、耐熱性、機械的強度、電気特性等の諸物性の更なる改善が要求されるようになってきている。これまで耐熱性に優れた絶縁材料として、例えば、特許文献１にはエポキシ樹脂、カルボン酸で変性されたアクリロニトリルブタジエンゴム、硬化剤、硬化促進剤、無機充填剤からなる接着剤組成物、カバーレイフィルムが示されているが、いまだ十分な難燃性を有していなかった。また特許文献２には、（ａ）ポリフェニレンエーテルと不飽和カルボン酸又は酸無水物との反応生成物、（ｂ）トリアリルシアヌレート及び／又はトリアリルイソシアヌレート、（ｃ）少なくとも一つのイミド環を含む臭素化芳香族化合物からなる硬化性樹脂組成物が示されており、難燃性の一層の向上を図るために、難燃助剤として酸化アンチモン化合物を（ｄ）成分として添加することが記載されているが、安全性に問題がある。酸化アンチモン化合物を含まない硬化性樹脂組成物では、１ｍｍもの厚みがあれば難燃性を示しても、２５〜７５μｍ程度の厚みでは多量のハロゲン系難燃剤を添加しなくてはならず、機械的性質の低下をもたらすものであった。したがって、高い難燃性と、高い機械的強度を持ち合わせるためには多くの厚みを必要とし、柔軟な樹脂成型体が得られないという問題を有している。 2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for higher density, smaller size, and thinner electronic components used in electronic devices. As a result, further improvements in physical properties such as heat resistance, mechanical strength, and electrical characteristics have been required for electronic component materials. As insulating materials having excellent heat resistance, for example, Patent Document 1 discloses an adhesive composition composed of an epoxy resin, acrylonitrile butadiene rubber modified with a carboxylic acid, a curing agent, a curing accelerator, and an inorganic filler, and a coverlay. Although a film is shown, it still did not have sufficient flame retardancy. Patent Document 2 discloses (a) a reaction product of polyphenylene ether and unsaturated carboxylic acid or acid anhydride, (b) triallyl cyanurate and / or triallyl isocyanurate, and (c) at least one imide ring. A curable resin composition comprising a brominated aromatic compound containing benzene is shown, and in order to further improve flame retardancy, an antimony oxide compound may be added as a flame retardant aid as component (d). Although described, there is a problem with safety. In the case of a curable resin composition containing no antimony oxide compound, even if it has a thickness of 1 mm, it exhibits flame retardancy, but if it has a thickness of about 25 to 75 μm, a large amount of halogen flame retardant must be added. The deterioration of the mechanical properties. Therefore, in order to have high flame retardancy and high mechanical strength, a large thickness is required, and a flexible resin molded body cannot be obtained.
本発明の目的は、上記従来技術の有する問題点を解決し、難燃剤および難燃助剤を含有することなく、または、該剤の含有量を極めて少なくしても、高い難燃性を発揮し、しかも高温下における寸法安定性に優れ、さらに薄いフィルム、シート、平板としても十分な機械的強度を有する耐熱性樹脂構造体を提供することにある。 The object of the present invention is to solve the above-mentioned problems of the prior art and exhibit high flame retardancy without containing a flame retardant and a flame retardant aid or even if the content of the agent is extremely low. And it is providing the heat resistant resin structure which is excellent in the dimensional stability under high temperature, and has sufficient mechanical strength also as a thin film, a sheet | seat, and a flat plate.
本発明者らは、かかる問題を解決するため検討した結果、ＬＯＩが２０以上のポリマーからなるフィルム、シート、または、平板である樹脂成型体であって、平均粒子径が０．０５〜２５μｍである無機粒子を樹脂成型体重量に対し１０〜９５重量％含有し、厚みが２５〜２００μｍ、引張強さが３０ＭＰａ以上、３００℃における熱収縮率が１０％以下であることを特徴とする耐熱性樹脂成型体によって上記目的を達成できることがわかった。 As a result of studying to solve such a problem, the present inventors have found that the resin molded body is a film, sheet, or flat plate made of a polymer having a LOI of 20 or more, and has an average particle diameter of 0.05 to 25 μm. Heat resistance characterized by containing certain inorganic particles in an amount of 10 to 95% by weight based on the weight of the molded resin, having a thickness of 25 to 200 μm, a tensile strength of 30 MPa or more, and a thermal shrinkage at 300 ° C. of 10% or less. It turned out that the said objective can be achieved by the resin molding.
本発明によれば、難燃性、高温下における寸法安定性に優れ、薄いフィルム、シート、平板としても十分な機械的強度を有している耐熱性樹脂成形体を提供することができる。このため、難燃性や難燃助剤を含有させる必要がなく、または、該剤の含有量を著しく低減できるといった効果を有している。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in a flame retardance and the dimensional stability under high temperature, and can provide the heat resistant resin molding which has sufficient mechanical strength also as a thin film, a sheet | seat, and a flat plate. For this reason, it is not necessary to contain a flame retardancy or a flame retardant aid, or the content of the agent can be significantly reduced.
本発明の耐熱性樹脂成型体は、ＬＯＩが２０以上のポリマーからなるフィルム、シート、または、平板である樹脂成型体である。該ＬＯＩが２０以上のポリマーとしては、例えば、メタ型芳香族ポリアミド、パラ型芳香族ポリアミド、ポリベンゾイミダゾール、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリアリレート、ポリパラフェニレンベンゾビスオキサゾール、ポリフェニレンスルフィドなどを好適に挙げることができる。なかでも、高耐熱性を有し、かつ高い強度が得られ、さらに世界的にも供給量が多く安定しているパラ系の芳香族ポリアミド、すなわち、ポリパラフェニレンテレフタルアミド、または、これに第３成分を共重合したポリパラフェニレンテレフタルアミド共重合体を用いるのがより好ましい。ポリパラフェニレンテレフタルアミド共重合体の一例として、下記式に示すコポリパラフェニレン・３．４’オキシジフェニレンテレフタルアミドが例示される。 The heat-resistant resin molded body of the present invention is a resin molded body that is a film, sheet, or flat plate made of a polymer having a LOI of 20 or more. Examples of the polymer having an LOI of 20 or more include meta-type aromatic polyamide, para-type aromatic polyamide, polybenzimidazole, polyimide, polyamideimide, polyetherimide, polyarylate, polyparaphenylenebenzobisoxazole, polyphenylene sulfide, and the like. Can be preferably mentioned. Among them, para-type aromatic polyamides having high heat resistance, high strength, and stable supply in the world, that is, polyparaphenylene terephthalamide, or It is more preferable to use a polyparaphenylene terephthalamide copolymer obtained by copolymerizing three components. As an example of the polyparaphenylene terephthalamide copolymer, copolyparaphenylene 3.4'oxydiphenylene terephthalamide represented by the following formula is exemplified.
本発明においては、上記樹脂成型体に、平均粒子径が０．０５〜２５μｍである無機粒子を樹脂成型体重量に対し１０〜９５重量％含有していることが肝要である。本発明者らは、これにより、難燃剤や難燃助剤を含有していないにもかかわらず、ＬＯＩが３０以上という高い難燃性を実現できることを見出した。上記樹脂成型体には、さらに高い難燃性を得るため、難燃剤や難燃助剤を含有させることも可能であるが、本発明においては、そうした場合でも、それらの剤の含有量を著しく低減することができるといったメリットも有している。さらに、本発明の樹脂成形体においては、高温における熱収縮が極めて小さく、寸法安定性が格段に向上していることがわかり、本発明に至ったものである。 In the present invention, it is important that the resin molded body contains 10 to 95% by weight of inorganic particles having an average particle diameter of 0.05 to 25 μm with respect to the weight of the resin molded body. The present inventors have found that this makes it possible to realize a high flame retardancy with a LOI of 30 or more, even though it does not contain a flame retardant or a flame retardant aid. In order to obtain higher flame retardancy, the resin molded body may contain a flame retardant or a flame retardant aid. However, in the present invention, even in such a case, the content of these agents is remarkably increased. It also has the merit that it can be reduced. Furthermore, in the resin molding of this invention, it turns out that the thermal contraction at high temperature is very small, and dimensional stability is improving remarkably, and it came to this invention.
無機粒子の平均粒子径が０．０５μｍ未満では、均一に分散させるのが難しいため取扱い性が悪く、平均粒子径が２５μｍを越えると、樹脂成型体の強度が低下する傾向にあり、特に樹脂成型体が薄いフィルムである場合、強度が低下しやすく、また、表面に凹凸ができやすく平滑性や美観を損なう恐れがある。 If the average particle size of the inorganic particles is less than 0.05 μm, it is difficult to disperse uniformly, so that the handleability is bad. If the average particle size exceeds 25 μm, the strength of the resin molded product tends to decrease. When the body is a thin film, the strength tends to decrease, and the surface tends to be uneven, which may impair smoothness and aesthetics.
また、無機粒子の含有量が１０重量％未満では、十分な難燃性や寸法安定性が得られない恐れがある。一方、該含有量が９５重量％を越えると、樹脂成型体の強度が低下する傾向にあり、特に樹脂成型体が薄いフィルムである場合、強度が低下するだけでなく、成型時に割れや穴が発生しやすくなりフィルム形成ができない恐れがある。無機粒子の含有量は好ましくは２０〜８０重量％である。 Further, if the content of inorganic particles is less than 10% by weight, there is a possibility that sufficient flame retardancy and dimensional stability cannot be obtained. On the other hand, when the content exceeds 95% by weight, the strength of the resin molded product tends to decrease. Particularly, when the resin molded product is a thin film, not only the strength decreases but also cracks and holes are formed during molding. It is likely to occur and film formation may not be possible. The content of inorganic particles is preferably 20 to 80% by weight.
本発明に使用する無機粒子としては、無機粒子としては、カーボン、アルミナ、タルク、雲母、カオリン、クレイ等を挙げることができる。また、これらは一種類を用いても、二種類以上を組み合わせて用いてもよい。 Examples of the inorganic particles used in the present invention include carbon, alumina, talc, mica, kaolin, and clay. These may be used alone or in combination of two or more.
また、上記無機粒子としては、リン片状（扁平状）であることが好ましく、リン片状の粒子が配向することにより樹脂成型体の強度を向上させることができるだけでなく、得られる樹脂成型体の平滑性も良好なものとなる。かかる理由からも、無機粒子として雲母またはリン片状のカーボン、特に雲母を用いることが好ましい。また、無機粒子は分散性を向上させるためにシランカップリング処理がされていてもよい。 In addition, the inorganic particles are preferably in the form of flakes (flat), and not only can the strength of the resin moldings be improved by the orientation of the scaly particles, but also the resin moldings obtained The smoothness of the film is also good. For this reason, it is preferable to use mica or scaly carbon, particularly mica, as the inorganic particles. The inorganic particles may be subjected to silane coupling treatment in order to improve dispersibility.
本発明においては、樹脂成型体の厚みは２５〜２００μｍであり、２５〜５０μｍが好ましい。該厚みが２５μｍ未満では十分な強度が得られない恐れがあり、また２００μｍを越えるものは、キャスティング法によりフィルム等を成形する場合、ポリマーが流れやすくなり、成形が難しくなる傾向にある。 In the present invention, the resin molded body has a thickness of 25 to 200 μm, preferably 25 to 50 μm. If the thickness is less than 25 μm, sufficient strength may not be obtained. If the thickness exceeds 200 μm, when a film or the like is formed by a casting method, the polymer tends to flow and the forming tends to be difficult.
さらに、本発明においては該樹脂成型体の引張強さが３０ＭＰａ以上、３００℃における熱収縮率が１０％以下である必要がある。引張強さが３０ＭＰａ未満では、電子材料への応用を考えた場合に強度が不十分であり、３００℃における熱収縮率が１０％を越える場合には、はんだづけなどによる熱により容易に素材が変形し、絶縁性能や導電性能が低下してしまう恐れがある。 Furthermore, in this invention, the tensile strength of this resin molding needs to be 30 Mpa or more, and the thermal contraction rate in 300 degreeC needs to be 10% or less. If the tensile strength is less than 30 MPa, the strength is insufficient when considering application to electronic materials. If the thermal shrinkage at 300 ° C exceeds 10%, the material can be easily deformed by heat from soldering. In addition, the insulating performance and the conductive performance may be deteriorated.
次に、本発明の樹脂成型体の成形方法について説明する。該樹脂成型体は、例えば、平板の場合は、射出成形やブロー成形、真空成形、圧空成形、切削加工によって製造することができる。また、フィルムやシートの場合は、フィルムキャスティングや樹脂延伸により容易に製造することができる。 Next, the molding method of the resin molding of the present invention will be described. For example, in the case of a flat plate, the resin molded body can be manufactured by injection molding, blow molding, vacuum forming, pressure forming, or cutting. In the case of a film or sheet, it can be easily produced by film casting or resin stretching.
上記のキャスティングによる成形についてより具体的に説明すると、例えば、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰ）に、ポリパラフェニレンテレフタルアミド等の芳香族ポリアミドを１〜１０重量％と、芳香族ポリアミドの重量に対して１０〜９５重量％の無機粒子を加え、６０〜９０℃に加温してそれらをＮＭＰ中に分散させる。次いで、厚みが、２５〜２００μｍとなるようにキャスティングを行い、１５０〜２００℃で乾燥し、その後流水処理した後１００〜１５０℃で乾燥することによって、該フィルムやシートを成形することができる。また、後の乾燥の際、フィルムやシートの皺を防ぐため、２辺もしくは４辺を枠によって固定しておくことが好ましい。 More specifically, the above molding by casting will be described in detail. For example, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 1-10% by weight of aromatic polyamide such as polyparaphenylene terephthalamide, aromatic polyamide 10 to 95% by weight of inorganic particles is added to the weight of the mixture and heated to 60 to 90 ° C. to disperse them in NMP. Next, the film or sheet can be formed by casting so as to have a thickness of 25 to 200 μm, drying at 150 to 200 ° C., then treating with running water and then drying at 100 to 150 ° C. In order to prevent wrinkling of the film or sheet during subsequent drying, it is preferable to fix two or four sides with a frame.
以下、本発明を実施例により更に詳細に説明する。尚、実施例中の各物性は下記の方法により測定した。
（１）厚み
ＪＩＳ Ｌ １０９６−９０に準拠した方法により、ディジマティック厚さ試験機を用いて織物測定用荷重（２４０ｇ／ｍ２）にて測定を行った。
（２）引張強さ
ＪＩＳ Ｋ−７１２７に準じて、サンプルの幅を２５ｍｍ、サンプル長を１００ｍｍとし、引張速度を１００ｍｍ／分にて引張強度を求めた。
（３）難燃性
限界酸素指数（ＬＯＩ値）をＪＩＳ Ｋ ７２０１に準拠した方法により測定した。
（４）乾熱収縮率
３００℃の高温雰囲気下に５分間暴露し、該フィルムの収縮率を測定した。
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, each physical property in an Example was measured with the following method.
(1) Thickness By a method according to JIS L 1096-90, measurement was performed with a load for fabric measurement (240 g / m 2 ) using a dimatic thickness tester.
(2) Tensile strength According to JIS K-7127, the sample width was 25 mm, the sample length was 100 mm, and the tensile strength was determined at a tensile speed of 100 mm / min.
(3) Flame retardancy The critical oxygen index (LOI value) was measured by a method based on JIS K 7201.
(4) Dry heat shrinkage The film was exposed to a high temperature atmosphere at 300 ° C. for 5 minutes, and the shrinkage of the film was measured.
［実施例１］
Ｎ−メチル−２−ピロリドン（以下、ＮＭＰ）に、平均粒子径が６μｍの合成雲母粒子（コープケミカル（株）製ＭＥ−１００）を２０重量％混合し、全重量の５重量％となるようパラフェニレンジアミンと３，４’−ジアミノジフェニルエーテル（帝人テクノプロダクツ（株）製、濃硫酸を溶媒として３０℃で測定した固有粘度が１．５）を加え、１０分間攪拌させた後、６０℃に加温して分散させた。次いで、最終厚みが３０μｍとなるようキャスティング厚みを調整し、キャスティング後、１２０℃で３０分乾燥し、その後流水処理した後、４辺を枠で固定して８０℃で１０分、さらに１２０℃で２０分乾燥させ、皺のない縦２０ｃｍ、横２０ｃｍの、粒子の含有量が２０重量％であるフィルムを成形した。結果を表１に示す。
[Example 1]
N-methyl-2-pyrrolidone (hereinafter referred to as NMP) is mixed with 20% by weight of synthetic mica particles having an average particle diameter of 6 μm (ME-100 manufactured by Co-op Chemical Co., Ltd.) so that the total weight becomes 5% by weight. After adding paraphenylenediamine and 3,4′-diaminodiphenyl ether (manufactured by Teijin Techno Products Co., Ltd., intrinsic viscosity measured at 30 ° C. using concentrated sulfuric acid as a solvent is 1.5), the mixture was stirred for 10 minutes and then heated to 60 ° C. Warmed and dispersed. Next, the casting thickness is adjusted so that the final thickness is 30 μm, after casting, dried at 120 ° C. for 30 minutes, and then treated with running water, and then fixed on the four sides with a frame, at 80 ° C. for 10 minutes, and at 120 ° C. The film was dried for 20 minutes, and a film having a wrinkle-free 20 cm long and 20 cm wide particle content of 20% by weight was formed. The results are shown in Table 1.
［実施例２〜３、比較例１〜２］
合成雲母粒子の含有量を表１のように変更した以外は、実施例１と同様にしてフィルムを作成した。なお、比較例１は合成雲母粒子を添加しなかった。結果を表１に示す。
[Examples 2-3, Comparative Examples 1-2]
A film was prepared in the same manner as in Example 1 except that the content of the synthetic mica particles was changed as shown in Table 1. In Comparative Example 1, no synthetic mica particles were added. The results are shown in Table 1.
［実施例４］
合成雲母粒子に代えてをカーボンブラック（大日精化工業（株）製ＭＰＳ−１１００Ｂｌａｃｋ）を用いた以外は、実施例１と同様にしてフィルムを作成した。結果を表１に示す。
[Example 4]
A film was prepared in the same manner as in Example 1 except that carbon black (MPS-1100 Black manufactured by Dainichi Seika Kogyo Co., Ltd.) was used instead of the synthetic mica particles. The results are shown in Table 1.
本発明の耐熱性樹脂成型体は、難燃性、高温下における寸法安定性に優れ、薄いフィルム、シート、平板としても十分な機械的強度を有しているため、誘電材料、絶縁材料、耐熱材料等として用いることができ、電気産業、電子産業、宇宙・航空機産業等の幅広い分野に応用することができる。 The heat-resistant resin molded body of the present invention is excellent in flame retardancy and dimensional stability at high temperatures, and has sufficient mechanical strength as a thin film, sheet, or flat plate. It can be used as a material, etc., and can be applied to a wide range of fields such as electrical industry, electronic industry, space / aircraft industry, and the like.
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